Process of hardening cellulose matter and resulting products



M 29,1938. c, CK T- 2,112,245

PROCESS OF HARDENING CELLULOSE MATTER AND RESULTING PRODUCTS Filed April25. 1936 INVENTOR- Chri opher' 12%1ug Y y g. 0% HJ TORNEY Fig. 4isadiagramm'atic Patented 29, 1938 UNITED STATES. I

PAT-ENT oF c-E raocns's or momma CELLULOSE Man. maammssunrme rnonnc'rs 7Christopher Luchhaupt, Jamaica, is. Y. Application April 2a, 1936, senNo. 15.929 c Olaimsr (c1. ii -'10) This invention relates to a method-o!hardening cellulose and kindred matter and products resulting therefrom.

An object this invention is the production of products 'of celluloseandkindred constituency possessing coefficients of enhanced hardness andenhanced correlated attributes, viz, increased tensile strength,increased flexural strength,"increased compressional strength,.etc.

objects of cellulose and kindred constituency possessingattributes ofwater-, -moisture-, oil-,

and/or other prooi'ness, and/or flre-prooiness,

and/or verminand other bacteriological-wooimegs. a

' I An object products oi! cellulose and kindred constituency Fesistantto weather deterioration, including 're-.

sistance to theefl'ects of the sun, and like ex- P051113- I v I Anotherobject of the invention is the production or productsfofcelluiose andkindred 'constituencyembodying one'or more of the above stated improvedqualities and/or with variant coloring eflect.

My invention comprises, in general, the treat- I form, illustratingcellulose matter treated pursuant to my process. the product representedin 4 this figure being typical of so streated natural cellyiose mattersuch as wood or other vegetable matter, pulp formed therefrom, etc.

Fig. 2is an elevational view, in diagrammatic torm, illustrating ahollow objector celluloseconstituency treated pursuant to .my process,the

indicated bottle being typical" of various'iorms 'otbottomiess as wellas bottomed obje'cta'the latter serving as a'bottle onpther container,

Fig. 3 is a perspective view, in form, illustrating a product formedpursuant to my process, the illustration typical of and the like.

viemfin elevation, in-

An object oi! the invention is the production of of the invention is theproductions! dicating certain essential steps n carrying outthe-immersion method of my my ntion.

Referring to the drawing illustrating typical products attained pursuantto my invention, and indicative of other products suitable to theattainment o! the purposes of my invention:

In general, my process comprises treating .objects of original naturalorartiflcia'l cellulose constituency, with terpin hydrate or equivalent,as-by immersion spraying or other suitable procedure whereby suchtreatment material penetrates the pores or interstices of such originalobjects andby impregnation action imparts the characteristics of greatlyimproved physical attributes and immunity to water, moisture, oilsand,otherchemicals, and .otherfattributes as appears more fullyhereinaiter.'

Preferably, pursuant-to my immersion procedure, the treatment materialis heated to a temperature of 1 1520;, and upward, in a suitable tankerother container, the object to be treated being immerse'din suchbath,and upon withdrawal therefrom, the treated object is passed through anatmosphere at elevated temperature, whereupon the product issubstantially complete.

Highly satisfactory results are attained by'immersing the object in'abath. of terpin hydrate,

CcHs(OH)2(CH:)(CaH1)H20. formed by heat-- ing terpin hydrate crystals orpowder in a'suit able container until the terpin hydrate melts,- i. e.,is dissolved in its own water of crystaliza- 'tion, the temperature ofthe conminer being maintained at 0., or .upward: Suchcontainerispreferably substantially closed relative to the outer atmosphere,suitable'provisionhbeing made for the charging of the object into suchcontainer for immersion into such bath, the object after immersion beingcontinued in an atmosphere of a temperature of at least 115 0.,

for a relativelyfshort time period, usual] but a few minutes;

My invention is applicable also for treating, objects of 'cellulose orkindredconstituency, such I as wood or other natural v etable matter,or,

jects by spraying artificial cellulose containing,

the stated treatment material upon such object.

suitable provision' being made for heating and,

.maintaining the treatment -material and the spray of thetreatmentmaterial'at proper eleyated temperaturai and, desirablyadditionally,

e v th ev faces 0! the object subjected ,to the spray. fabricatedproducts, such as corrugated board .mersion procedure andsprayingprocedure, to

It'ifadvantageous, in employment oi my intprovide that the treatment,m'aterialin excess 01' that absorbed by the treated object, bereturned, i. e., in fluid or powder at elevated temperature to the bathor other reservoir containing the supply 01' the treatment material. I

Illustrations of objects of suitable constituency applicable totreatment pursuant to my process. are: wood and other plant growths,inclusive oi vegetable matter, objects made of pulps of paper, wood,vegetable and other cellulose or cellulosecontaining pulp; such assheets, board, molded 1' objects oi such material such as bottles, boxesand other containers, tubes or other hollow rods, solid rods, cellularstructures, artificial silk, cellulose textiles, etc.

By my process, the object treated is enhanced in hardness, that is'tosay, increased in tensile strength, fiexural strength, compressionstrength,

and other, physical characteristics imparting strength and rigidity,etc.

Predicated upon products which I have produced pursuant to myprocess-and upon the results of tests thereon, suclr hardening and otherenhanced attributes are eflected by the penetration of terpinhydrateinto and within. the original cellular and/or porous structure of thetreated material and impregnation of the treat ,ment material throughoutthe treated'material,

fdislodgement and'expulsion of moisture and other "constituents ofnatural or artificial cellulose matter, which constituentsnormallysubiect cellulose matter to rot or other deterioration, attackby, vermin, etc. l

Pursuant to my process, green wood may be cured by impregnation of mystated treatment material, as herein set forth, the curing operationbeing completed in the course of a brief time duration,'which may beeven less than one hour.

m process isoapplicable conjointly with the" dualtreatment withfortifiers affording the at- 1 tributes of water-proofness,fire-proofness, vermin resistance and the like. As a fortifler forwater-proofness, I cite aluminum subacetate,

aluminum steara'te, calcium stearate and the like. Such fortifier may beadded, as a powder,

to the melted terpinhydrate.

Aluminum subacetate, as a iortifier renders the resulting product fireresistant, that is to say, non-self-combustible. J

Utilizing as a fortifier, .cupric stearate, added to the meltedterplnhydrate, the resulting prodnot is water-mooted, and resistant tobarnacles, termite and other vermin attack as well as ininhardness andattendant physical atcreosote orthe like mayalso be added to the. jmelted terpinhydrate, rendering the resulting poses.

, Montan wax carnauba'wax, when employed as fortifiers withterpinhydrate, eflect electrical insulating qualities to wood and other.natural attributes of moisturefire-resistance, bil-repellance,vermin-proofness,

vegetable matter, wood pulp and other cellulose matter, natural,artificial and fabricated. 7

If desired, waxes and the like may be, added to the melted'terpinhydrate, such as 'carnauba wax, ceresin wax, etc., .to impart apermanent source in polish or gloss, and function to control ,byproportional quantity the degree of pliability.

Triphenyi phosphate may be employed as a ,fortifler for rendering. theproduct water-proof,

and fire-proof as well as of enhanced hardness, etc: Zinc acetate, as afortifier, enhances fire resistance and zinc stea -ate as ;a fortiflerenhances water-proofness.

A product of superior qualities as building material-is derivedfromply-wood and like laminated cellulose constituency, possessing the]strength of natural wood, with moisture-, waterfire-, vermin-- and otherdesired proofness.

Textiles formed of rayon and other synthetic cellulose matter may besimilarly treated for resistance against water alzvsorptiori, resistanceagainst combustion, the texture of the resulting textile product beingcontrolled in pliability by the addition of suitable plasticizers. Cedaroil or like material, particularly useful for preservation of woolgarments and the like against moths and other vermin, may beinchrporated with my melted treatment material, whereby the resultingproduct is premanentlyimpregmated with such source a! cedar or likeatmosphere. cellulose constituency, thus treated, may serve as cedarchests, moth-ba'gsf and the like..

- Color, as desired, may .be imparted to the treated article, by addingsuitable color, such as analine, vegetable,,miner'al andother dyes,pigments, etc/to the melted terpinhydrate.

-'Sheets, board, corrugated board, bags; cups and the like, ofpresent'commercial and other approved individual products of paper andother cellulose constituency, when treated pursuant to my invention, aretransformed into strong and rigid objects, possessing optionally any ofthe stated additional attributes. Tubes, rods and the like of originalpaper or wood pulp or other cellulose constituency are transformed intoma- 1 terial suitable for commercial uses comparable Boxes and the like,of paper or other in strength, weight supporting qualities, resistanceagainst crushing, etc., to like attributes of natural wood, metal andthe like, with the added and water-prooiness,

electrical, heat and sound insulating, etc., as

optionally desired. Such treated articles mayusefully serve in sheet orboard as pie plates, dishes and table ware, wall board, wall panels,shingle material, roofing covering, floor covering, etc., and in hollowforms as bottles, glasses and the like, flower and other pots, conduitsfor elec-.

trical wiring, waste and other fluid conduits, etc. So-ca'lle'dregenerated celluloses and the like,

the so-termed Cellophane being typical, when l treated as above set out,retain transparency as well as being enhanced in mechanical strength,and rendered water-, moistureand other fluid- ,proof, etc., serving assubstitutes for panes of glass, glass bottles and other containers, etc;If

j desired, a degree of translucency, had by selection of proper coloradded to the treatment material, may be imparted by my process.

, Rig. 1 illustrates at III a generally solid article typical ofsubstitute lumber, board, tile, block or other unit for wall,lfioor,ceiling, etc., of buildings,

vehicles such as automobiles. airplanes, ,toyvehicles, etc.,steambcata'lifeboata canoes, rowarias-is boats, and other navigationvessels, etc., treated. pursuant to my invention as elsewhere hereinmore specifically set forth.

Fig. 2 illustrates at ii an object, specifically.

treatment material, constituted as more specifically set forth elsewhereherein, which bath may be maintained at the desired elevated temperatureby means of a heating element shown diagrammatically at l5,advantageously of electrical type, the electrical wiring being indicatedat lIa. Such tank is substantially wholly closed to the outeratmosphere, as by a cover, canopy or other I form of closure indicatedat i6, suitable means'of entry as at Ma and .ofexit as at iib for the:objectato be treated,as forinstance by continuous operation uponaseriesof objects-indicated at ll tobe immersed intoand conveyed through suchbath- I, as by means of an endless chain i8 of conventional or otherapproved type, suitable mutually spaced breaker rolls being indicated ati9, 20, within such tank l3.to effect the low- .ered travel of suchendless chain ll to fully 1m:-

merse such objects l'l below. the level a of .such bath ll; suchcomplete'immersion may be positively had by: the employmentof the supplemental rolls indicated at 2|, 2|. Breaker rolls are indicatedat-suitable locations 22 exteriorly' of'thetank I: for the desiredtravel of the endless chain l8 and the-propulsion'of the same.

Tubesand like pre-shaped objects of paper stock, paper pulp, may betreated pursuant to my invention and transformed into curtain andlikesupporting rods, waste piping, water and I other distribution conduitsand the like.

In general, pre-shaped objects of natural cellulose matter in whole orin part fabricated into products of paper, paper pulp, wood pulp, andthe 50 like, may be transformed by utilization of-my inventionrintoobjects possessing controlled enhanced tensile, flexural andcompression'strength in substitution of metal and like normally rigidmaterials, or other less rigid; materials such as celluloid, plastics,etc. a

Characteristic properties pursuant to my invention reside in thecomplete closure of they normal interstices of the surfaces of. theoriginal material and complete closure of inner cells and/or voids, bythe impregnated terpin hydrate, with-or .without any stated or 'othersuitable i'ortifier. or i'ortii'iers further, by

my process the surfaces of the treated product are rendered whollysmooth. If an external finish is desired, the treatedproduct-requiresbut simple finishing operation, such as a's'ingle sanding operation, tofully prepare the object for any surface-finish'such' as by the-mediumof shellacs, .or varnishes, or oil paints of turpentine, lin-. seed oil,benzene,"mineral spirits as vehicles, or

I lacquers such as of nitrocellulose, acetylcellulose and the like, orof other soluble "cottons, phenol derivative anti 'otlier syntheticresins, casein,

paints, etc. I Y

My treatment material may tie-employed as a nation. pursuant to primingcoat for the stated materials, rendering. the treated objectwater-proof, etc., applicable for objects subject to water immersidn,steam and other moisture exposure, etc.

My treatment material possesses also adhesive properties while in tackystatus, thus enabling component parts to be formed of wood, paper orwood pulp, or the like, thecomponent parts after 7 being suitablytreated, as aforesaid, for the above stated attributes, are readilyformed into the 10 desired final product by mere echanical assembly. a

A characteristic of my inventionresides in the feature of impartingnon-warping and nonshrinking attributes to the pr'e-shaped producttreated pursuant to my process.

A further characteristic resides in the attribute that the treatedproduct preserves permanently the contour inward as well as outward andall dimensions of the original pre-shaped object treated.

Further objects capable of being produced pursuant to my invention areplates for baking, transporting and serving pies, cakes and the like"produced from suitably molded i. e. pre-shaped cel- 2 lulose containingmatter. 8}

.Further objects of sheet form produc by 'my invention may be utilizedin substitution of felt or the like as sound adeners, as in applicationto-metal or otherwa 1 parts of automobiles, and the like, liners, wallinsulation and the like.

Pursuant to my invention, the degree of the' respective'attributes of.hardness and/or wate'r-proofness and/or oil-proofness and/or soundinsulation and/or fire-proofness and/or electrical insulation in use asdielectrics is controlled by regulating the temperature of the bath ofthe treatnient material inexcess of 115 C., the higher the temperaturethe greater the degree of im- .parted stated attributes and the lowerthe tem- 40 perature in excess of 115 C.:the lesser the'degree ofimparted stated attributes,. and/or by .regulating the time period oftreatment, the longer the period of treatment the greater-the degree ofimparted stated attributes, and vice versa,

and/ or by selection of added fortifiers of selected density, thegreater the density of the fortifier or fortifiers, the less the extentof penetration 'andthe less attendant degree of the imparted .statedattributes.

By my treatment, balsa wood and like natural" cellulose matter normallyof non-uniform hardness and/ or variant porosity have imparted there-.to when treated pursuant to my method uniform hardness and full absenceof pores and other of objects treated" Balsa wood when treated pursuantto my invention is rendered germ-free and germ-proof, as well aswater-proofed. Balsa wood and like woods may be-treated for completeimpregnation or partial impregnatio or mere surface imprege proceduresabove set forth. White wood,'when treated pursuant to myf inventifulfills the requirements of material for heels for ladies shoes, etc;the product after immersion bonds readily with coating ma,- teriai suchas varnishes. lacquers, etc. by mere. application of the same; Dyes, asabove set out.

may be incorporated with my treatment material, thus affording coloringcoincidentlywith imparting the improved attributes as above enumerated,the product being fully finished as a result of my statedimmersiontreatment. per se. vShould any high finish be desired ofproducts treated pursuant to mrmethodthc same is attafned by meresanding and/or bufling ,or like simple procedure. I

Objects comprising cellulose when treated with certain fortifiers withmy .treatment material arerendered proof against alcohol and/or againstethyl" acetate, and/or against butyl acetate,

and/or against amyl' acetate, and/or methyl or ethyl or butylcellosolve, and/or other materials 01 like hydrocarbon constituency.Examples of such type of fortifiers are strontium glycerophosphate withlike.

The above enumerated fortiflers attaining water-proofness impart alsothe attribute of milk proofness. Strontium giycerophosphate utilized asa fortifier with my treatment, material imparts proofness with respectto carbon tetrachloride andalso with respect to turpentine and a largenumber of other hydrocarbons. 20

above, attain the above recited attributes attended with substantiallyno tendency of brittleness. Objects treated pursuant to my invention aresubstantially devoid of tendency to split, are

readily clear bored by any usual or other appropriate boring tool,readily sawed, cut or otherwise severed, readily planed, readily piercedby nails or screws, readily'shaped by shaping t0ols,.

all, without splitting, without surface checking and/or other defectsimparted to the treated material by the above operations. In operationsof sawing, cutting or other severing the severed faces are finishedsmooth, free from irregular or jagged edges and free from loose fibersor fragments of the severed material; in fact, the severed faces attaina polished surface by the severing operation, per se.

As indicative of the nature of hardness, coupled with increased tensilestrength, increased fiexural strength, increased compression strength, Icite the following illustrations:

Commercial 20 pound krai't paper .under the Mullin' test having anaverage rupture strength of the order of 40 pounds per square men, whentreated pursuant to my invention has imparted thereto arupture strengthof the order of other;- permanent deformation of the material.

The elasticity of the product imparted by my addition of a .paraflln waxand the treatmen'tmaterial functions to restore. the object to itsformer configuration upon release of such imposed load.

I A characteristic of my process resides inv the I attainment ofimproved hardness and attendant improved tensile, flexural and.compression" strengths imparted to the object treated, wholly withoutsubjecting the treated article to compression treatment, yieldingproducts pursuant to my method superior to present commercial acceptableplastics and the like, and obviating by my process molds, presses, etc.,necessary in stated treatment materials, terpinhydrate alone andterpimhydrate with one or more iortiilers selected to impart thedesired. improved particular qualities. h

My invention is also applica e generally to porous structures, such asCel otex, artificial wall boards, etc.

Whereas, I have described my invention by reference to specific formsthereof it will be understood that many changes and modifications may bemade without departing from the spirit oi the invention.

I claim:

l. The method 6f imparting enhanced hard- .ness to porous cellulosicmaterial, which comprises subjecting the -same to terpin hydrate at atemperature at or above the melting point of terpin hydrate.

2. The method of imparting enhanced hardness -to porous celluiosicmaterial which comprises subjecting the same to immersion in terpinhydrate at a temperature at or above the melting point of terpinhydrate.

3. The method f imparting enhanced hardness to a preshaped porousc'ellulosic object which comprises subjecting the same to a spray ofterpin hydrate at a temperature at or above the melting point of terpinhydrate. 4.-The method of imparting enhanced hardness to porouscellulosic material which comprises subjecting the same to melted terpinhydrate and controlling the degree of hardness by regulating thetemperatureof the treatment and regulating the time period of treatment.

5. The method of imparting enhanced hardness to a preshaped porouscellulosic object which comprises subjecting the same to immersion interpin'hydrate at a temperature at or above the melting point ofterpinfhydrate and withdrawing the thus treated cellulosic object fromsuch immersion into an atmosphere of elevated temperature.

6. An object made from porous cellulosic material, said cellulosicmaterial having its original interstices impregnated with solid terpinhydmte'.

- CHRISTOPHER ,LUCKHAUPT.

